DE1594824C3 - Use of new stilbenyl-1,3,4oxdiazole derivatives - Google Patents

Description

The present invention relates to the use of new stilbenyl-1,3,4-oxdiazole derivatives as optical Brightening agents for organic materials.

CH = CH

where A | stands for a phenyl, naphthyl, diphenylyl, styryl, stilbenyl, thienyl, 2-benzoxazolyl or 2-naphthoxazolyl radical, B is a divalent bridge member from the series phenylene, furoylene and thienyl, A _{x is} a phenyl , Diphenylyl or naphthyl radical, R stands for hydrogen, halogen, an alkyl, phenyl, carboxyl, sulfonic acid, Hy-Aus of the German patent specification 932 184 and the British patent specification 896 219 oxdiazole derivatives which can be used as optical brighteners are already known . New oxdiazole compounds have now been found which, due to the nature of the conjugated aromatic system which is bound to the oxdiazole ring, have a main absorption maximum that is noticeably shifted into the long-wave range compared to the previously known compound. The application-related consequences of this result in significantly higher maximum effects and unexpected increases in the yield of such brighteners.

These new oxdiazole derivatives correspond to formula

hydroxyl or amino group and their substitution products or functional derivatives, and terminal phenyl nuclei in the general formula can contain one or two substituents R, m, η and ρ also representing the values 1 or 2.

Under the above definition, compounds of the formula come into consideration in particular

N N

C-

-N

-A ₂

correspond, in which A _{2 is} a phenyl, naphthyl, diphenylyl, styryl, stilbenyl, thienyl, 2-benzoxazolyl or 2-naphthoxazolyl radical and a terminal phenyl nucleus has one or two substituents from the series alkyl, carbalkoxy, may contain alkoxy or halogen, B is a divalent bridge member of the series, means 2,5-Furoylen 2,5-thienylene or 1,4-phenylene, a a door _Jt Naphlhylrest. a diphenylyl radical or a phenylresl which can contain a substituent from the series consisting of alkyl, carbalkoxy or halogen, and m, η and ρ stand for the numbers 1 or 2.

Another basic type according to general formula 1 corresponds to the formula

V-CH = CH- ^ f V-C '

C C

N N

in which A is a phenyl, naphthyl, styryl, stilbenyl, thienyl, 2-benzoxazolyl or 2-naphthoxazolyl radical and B is a divalent bridge member from the phenylene, furoylcn and thienylene series and m and π are the values I or 2 is assigned and the radicals R is a substituent from the series hydrogen, halogen, alkyl, phenyl. Carboxyl, sulfo. Represent hydroxyl or amino groups and their substitution products or functional derivatives.

Possible phenyl radicals within the radical A can also have one or two substituents R, within the Bridging member B possible phenylene radicals can also have a radical R with that given above Contain meaning. Under the term given above, the substitution product or functional In addition to the substituent groups mentioned directly there, derivatives are also to be understood as such that are directly sub-

5 '6

are statistically or functionally derivable, i.e. ζ. B. in addition to amide, alkyl sulfone, aryl sulfone groups; Phenoxy

Alkyl groups also haloalkyl, hydroxyalkyl, oxyalkoxy groups; besides amino groups

Cyanoalkyl, carboxyalkyl, phenylalkyl, etc. groups, including alkylated, arylated and acylated amino groups,

pen; in addition to phenyl groups, also alkylphenyl, halo urethane and urea derivatives, triazinyl derivatives

genphenyl, alkoxyphenyl, carboxyphenyl, etc. 5 vate and similar, insofar as they meet the condition of the

Groups; in addition to carboxyl groups also meet carboxylic acid non-chromophoric characters,

ester-, carboxamide-, carboxonitrile-, car- Among the new Stfl \ jenyl-1,3,4-oxdiazole derivatives

acid hydrazide and similar groups; in addition to formula 1 and 3, there are those of the following

Sulpho groups and sulphonic acid ester and sulphonic acid formulas especially mentioned as examples:

R ₂ R ₁ R ₂ Ri R ₂ R ₁ R ₂

CH = CH

CH = CH

Il

N-

-N

CH = CH-

CH = CH

CH = CH

C-CH = CH- <X = A

CH = CH

/ ¹ V

N-

- CH = CH

CH = CH

R ₅

• N-c c-

N-

R ₅

N N N

0

R ₄

CH = CH-

R ₆

R ₊

R ₅

N N N N

HC CH 0 R _n

C C - C C - C

Il Il \ / Il

N N 0 N-

/ ^H V

cH =

R ₃

-N

CH = CH

O HC CH

/ \ Il Il / \ _{/ y} \ ν cc — cc — cc— s / ^

Il Il \ / Il

N N S N N

CH = CH

(14)

(15)

(16)

(17)

In these formulas, R ₁ and R _{3 are} each a sulfone or aryl sulfone group, or an acyl group

Resle, which are identical or different and each optionally substituted one or 1,3,5-triazinyl radicals

Hydrogen atom, a halogen atom, a straight-chain amino group, also R ₂ , R ₄ to R ₆ radicals,

or branched alkyl group, a phenyl group, unites: 30 which are identical or different and each have a hydrogen

Haloalkyl, hydroxyalkyl or cyanoalkyl group, atom, a chlorine atom, an alkyl group, a free

a nitrile or hydroxyl group, an alkoxy, or neutralized sulfonic acid group (--SO ₂ O-Kat-

Aralkoxy or phenoxy group, a carboxyl group, 'ion) or a sulfonic acid amide group,
a carboxylic acid ester, carboxamide or car are of preferred importance in the context of

bonsäurehydrazidgruppe, a sulfonic acid, sulfone ·· 35 present invention stilbenyl-1,3,4-oxdiazole-Deri-

acid ester or sulfonic acid amide group, an alkyl derivative of the formulas

• V

CH = CH

N-

-N

Il

-N

(18)

/ V

CH = CH

c-c

-N

CH = CH

y ν

U ₂ (19)

in which A, B, m and η the meaning given at the beginning alkyl or aryl groups substituted carboxylic acid

tion, and U, Uj and U ₂ mean the same or amide group.

are different and can each have a hydrogen atom, a specific connecting group of interest

Carboxylic acid ester group having at most 18 carbons is represented by the following formulas

Substance atoms, such as carboxylic acid alkyl or alkoxy, are:

alkyl, alkenyl, aryl or aralkyl ester groups or compounds of the formula

an optionally by alkyl, aralkyl, cyclo-

CH = CH

CH = CH

(20)

wherein R ₇ and R _{8 are the} same or different and represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, a carboxyl group, a carbalkoxy group with up to 4 carbon atoms in the alkyl group, a chlorine atom, a phenyl group or an Aflcoxygruppe with 1 to 4 carbon atoms .

509628/304

1 515

Compounds of the formula

CH == CH - <

> C N-

C-

Ii

-N

ίο

wherein the radicals R *, hydrogen atoms, alkyl groups with 1 to 6 carbon atoms or alkoxy groups with 1 to 4 carbon atoms or one radical R ,, represents a phenyl group or a 2-benzoxazolyl group, while the other radical R ... represents a hydrogen atom, or the two radicals R ,, together with the phenyl radical. on which they stand, form a naphthyl radical.
Compounds of the formula

CH = CH

C —CH-CH-

il

R,

wherein R _{10 represents} a hydrogen atom, a chlorine atom or a alkyl or alkoxy group, each with up to 4 carbon atoms, or a phenyl group.
Compounds of the formula

CH = CH

wherein R _{11 represents} hydrogen, a carboxyl group, or a carbalkoxy group with up to 4 carbon atoms in the alkyl group and R, _{2 represents} hydrogen, an alkyl group containing 1 to 4 carbon atoms or a phenyl group.
Compounds of the formula

CH = CH

N-

-N

wherein R _n is a Wasserstoffalom, a carboxyl group or a carbalkoxy group with 1 to 4 carbon atoms in the alkyl moiety, and R ₁₃ represents hydrogen, a carboxyl group, a carbalkoxy group mil 1 to 4 carbon atoms in the alkyl moiety, a 2-benzoxazolyl group or a phenyl group the compounds of the formula

wherein R, 4 represents hydrogen, an alkyl group containing 1 to 4 carbon atoms, a phenyl group or a styryl group. Compounds of the formula

CH CH

> - C C

il Il

N N

_14th

wherein Rj is ₄ hydrogen, an alkyl group containing 1 to 4 carbon atoms, a phenyl group or a

t ^ ägfuppe

The new Stitbenyl-13,4-oxdiazo derivatives can be called by various methods known per se put tSbrdea.

1515

A generally applicable manufacturing process is e.g. B. is that one for the production of connections the formula I an Aeylhydru / in the formula

A.

CII CH

O / NH - O / - «Bfcrrr- -C
Il O
\ ^{/ f} / - Il
N- R. HN \
c- -N

-A ₁

(27)

in which A _x , A ₁ , R, B, m, η and ρ have the meaning given above, subjected to the ring closure reaction to give the corresponding 1,3,4-oxdiazole derivative by treatment with excess thionyl chloride at elevated temperatures.

Compounds of the formula 2 are obtained quite analogously by adding an acylhydrazine of the formula

A, - CH - CH

NH -

C C-

! I Il

N N

• A,

(28)

where A _r A ₂ , B, m, η and ρ have the meaning given above, subjected to the ring closure reaction to give the corresponding 1,3,4-oxdiazole derivative by treatment with excess thionyl chloride at elevated temperatures.

In somewhat more detailed notation for connections represented by the formula 3, there is such a manufacturing process, for. B. in the fact that you either a stiibencarboxylic acid halide, preferably a chloride, of formula 29 with a hydrazide of

Formula 30 or a stilbenecarboxylic acid hydrazide of the formula 31 is reacted with a carboxylic acid halide (preferably chloride) of the formula 32 to form the acylhydrazine of the formula 33 and this is then subjected to ring closure to form 1,3,4-oxdiazole. This reaction sequence can be shown schematically as follows, where A, B, m and η in formulas 30, 32 and 33 have the meaning given under formula 3:

C)

CH = CH

(29)

Hal H ₇ N - HN

R O

" ^V -CH = CH- ^ f ^/ VC \ - / \

NH hN

H Hai O

(33)

- H shark

(30)

NH - NH, Hal

C-fB)

(32}

/ \
C C-

Il Il

N N

N-

/ \
C C-

Il 1!

N N

A.

\
C.

Ii

—N

In this way you can have both symmetrical and asymmetrical connections of the Fonnel 3 arrive.

Compounds of formula 3 with a symmetrical structure, in which A represents a stilbenyl radical, are obtained for example, that a stiibencarboxylic acid halide of the formula 29 with hydrazine. Hydrazine

1515

Ϊ4

hydrate, a salt of hydrazine or a dihydrazide of the formula 34, in which B, m and η have the meanings given at the beginning, according to the following scheme:

R. K
/ i - \ O H ₂ N- O (34) O NH ₂ O R. -CH = CH- ^) Hal " ^x c
-HN NH - Hal (29)

(29)

CH = CH
(35)

NH

HN

In a very similar manner, one can obtain the same type of compound 35 by converting 2 moles of a stilbene carboxylic acid hydrazide unit 1 mole of an acid chloride B (COHaI) _2. The diacylhydrazine of the formula 35 obtained by one of these routes, in which B, m and η have the meaning given at the beginning, is then subjected to ring closure to form 1,3,4-oxdiazole.

The reaction of the acid halides of the formulas 29 and 32 with hydrazine, hydrazine hydrate, salts of hydrazine or the carboxylic acid hydrazides of the formulas 30, 31 and 34 to give the acylhydrazines of the formulas 33 and 35 can be carried out in the presence of a tertiary nitrogen base at temperatures of about 50 to 150.degree are executed. It is recommended that tertiary nitrogen bases having not too low boiling point, preferably those whose boiling point is at least 100 ⁰ C, to use, for example N, N-diethyl- or Ν, Ν-dimethylaniline. Cyclic tertiary nitrogen bases such as quinoline and especially pyridine bases such as pyridine itself and alkylpyridines with low molecular weight alkyl radicals such as 2-, 3- and 4-methylpyridine (picolines), ethylpyridines or mixtures of such pyridine bases prove to be particularly advantageous.

Surprisingly, it has been shown that the reaction to the acylhydrazines of the formulas 33 and 35 in high-boiling, inert, slightly polar to non-polar organic solvents, such as o-dichlorobenzene or chlorobenzene in the presence of the stoichiometrically necessary amount of pyridine bases at about 50 to 150 ° C is possible, the subsequent ring closure to 1,3,4-oxdiazole without intermediate separation of the acylhydrazine by dropping in slightly more than the stoichiometrically necessary amount of thionyl chloride at temperatures between 120 and 220 ⁰ C, preferably at the boiling point of the reaction mixture very quickly and smoothly can be made. This possibility was noticeable and could not be foreseen, as, according to general experience, in comparable cases an uncontrollable reaction of the thionyl octaloride with the stilbene double bond was to be expected.

With the stflbenyl-U, 4-oxdiazole derivatives of the formula 1 obtained by the process described

NH

rr — HN

- (2). ... H ₂ O

If desired, further reactions, likewise leading to compounds according to formula 1, can be carried out be made, i.e., certain substituents can also be added subsequently in the respective Basic body are introduced. For example, you get to water-soluble derivatives if you

a) the stilbenyl-1,3,4-oxdiazole derivatives of formula 1 sulfonated, e.g. with sulfuric acid monohydral, chlorosulfonic acid or with sulfur trioxide containing Sulfuric acid, if necessary in the heat, and then the sulfonic acid group converted into the corresponding salts with organic or, preferably, inorganic bases;

b) one or more primary or secondary amino groups of the stilbenyl-l, 3,4-oxdiazole derivatives of Formula 1 with sultons, e.g. B. with propane sultone or butane sultone at elevated temperature in the corresponding alkylsulphonic acid derivatives:

c) one or more primary amino groups of the stilbenyl-1,3,4-oxdiazole derivatives of the formula 1 with aldehyde bisulfite compounds, e.g. B. with formaldehyde-alkali bisulfite converted into the corresponding f.j-methanesulfonic acid derivatives;

d) one or more primary amino groups of the stilbenyl-1,3,4-oxdiazole derivatives of the formula 1 with alkyl or aralkyl sulfonic acids such as ζ. Β Bromoethanesulfonic acid or benzylchloride sulfonic acid converts;

e) one or more primary or secondary amino groups or hydroxyl groups of the stilbenyl-1,3,4-oxdiazole derivatives of the formula 1 are linked via s-triazin-2-yl bridges with phenolsulfonic acids or anilinesulfonic acids;
in one or more hydroxyl groups dei stilbenyl-1,3,4-oxdiazole derivatives of the formula 1 with alkylene oxides, such as ethylene oxide or propylene oxide or with polyalkylene ether-monohalogenides, a polyalkylene ether chain long enough for water solubility to be introduced;

g) one or more capable of quaternizing Groups of the Stflbrayl-1,3,4-oxdiazole derivatives of formula 1 with quaternizing agents, wi z. B. methyl iodide, dimethyl sulfate, benzyl chlorine

1515

or toluenesulfonic acid alkyl esters in the heat. optionally under pressure, reacted;
h) one or more haloalkyl groups of the stilbenyl-13,4-oxdiazole derivatives of the formula 1 with tertiary bases, such as. B. fyridine converted into the corresponding quaternary derivatives.

The new optical brighteners described at the beginning Composition in the dissolved or finely divided state have a more or less pronounced fluorescence. You can optically brighten the most diverse high molecular weight or low molecular weight organic materials or materials containing organic substances are used will.

For this purpose, for example, without the following list being in any way limiting to this should be expressed the following groups of organic materials, as far as an optical Lightening of the same comes into consideration, to name:

I. Synthetic organic high molecular weight or higher molecular weight materials.

a) Polymerization products based on organic compounds containing at least one polymerizable carbon-carbon double bond, ie their homopolymers or copolymers and their aftertreatment products such as crosslinking, grafting or degradation products, polymer blends, etc .. for which, for example, may be mentioned:
Polymers based on ", / ^ - unsaturated carboxylic acids, in particular acrylic compounds (such as, for example, acrylic esters, acrylic acids, acrylonitrile, acrylamides and their derivatives or their methacrylic analogs), of olefin hydrocarbons (such as, for example, ethylene, Propylene, isobutylene, styrenes, dienes such as butadiene, isoprene, i.e. also rubbers and rubber-like polymers, also so-called ABS polymers), polymers based on vinyl and vinylidene compounds (such as vinyl esters, vinyl chloride, vinyl sulfonic acid, Vinyl ethers, vinyl alcohol, vinylidene chloride, vinyl carbazole), of halogenated hydrocarbons (chloroprene, highly halogenated ethylene), of unsaturated aldehydes and ketones (e.g. acrolein, etc.), of allyl compounds, etc., graft polymerization products (e.g. by grafting on vinyl monomers) , Crosslinking products (for example by means of bifunctional or polyfunctional crosslinkers such as divinylbenzene, polyfunctional allyi compounds or bis-A cry! compounds or by partial degradation (hydrolysis. Depolymerization) or modification of reactive groups (e.g. esterification, etherification, halogenation, self-crosslinking) are obtainable;

b) other polymerization products such. B. obtainable by ring opening, e.g. B. polyamides of polycaprolactam type, also formaldehyde polymers, or polymers both via polyaddition as well as polycondensation are available such as polyethers, polythioethers, polyacetals. Thioplasts;

c) Polycondensation products or precondensates based on bi- or polyfunctional compounds with condensable groups, their homo- and mixed condensation products and products the aftercare, for which, for example, are mentioned:

Saturated polyester (e.g. polyethylene terephthalate) or unsaturated (e.g. maleic acid dialcohol polycondensates and their crosslinking products with polymerizable vinyl monomers). unbranched as well as branched (also based on higher alcohols such as alkyd resins), Polyamides (e.g. hexamethylene diamine adipate), maleic resins, melamine resins, phenolic resins (Novolaks), aniline resins, furan resins, carbamide resins or their precondensates and analogue built products, polycarbonates, silicone resins, and others:

d) Polyaddition products such as polyurethanes (crosslinked and uncrosslinked). Epoxy resins.

II. Semi-synthetic organic materials such as. B. cellulose esters or mixed esters (acetate, propionate). Nitrocellulose, cellulose ether, regenerated cellulose (viscose, copper ammonia cellulose) or their Aftertreatment Products, Casein Plastics.

III. Natural organic materials of animal or vegetable origin, for example Based on cellulose or proteins such as wool, cotton. Silk. Bast, .'ute, hemp, furs and hair. Leather. Wood mass in fine distribution. Natural resins (such as rosin, especially paint resins), also rubber, Gutta-percha, balata, as well as their aftertreatment and modification products (hardening and Cross-linking), degradation (hydrolysis, depolymerization, grafting, modification of reactive groups (Acylation, halogenation, crosslinking, etc.).

The organic materials under consideration can be in the most varied of processing states (Raw materials, semi-finished products or finished products) and aggregate states are available. You can once in the form of the most varied of shaped structures, d. H. so z. B. predominantly three-dimensional extended bodies like blocks. Plates. Profiles. Pipes, injection moldings or the most varied Workpieces, chips or granulates, foams; predominantly two-dimensional Bodies such as films, foils, lacquers, tapes. Coatings. Impregnations and coatings or mainly one-dimensional bodies like threads. Fibers, flakes, bristles. Wires. The said On the other hand, materials can also be in the most varied of homogeneous states in unshaped states and inhomogeneous forms of distribution and states of aggregation exist, e.g. B. as a powder. Solutions. Emulsions. Dispersions. Latices (examples: lacquer solutions, polymer dispersions). Brine. Gels, putties. Pastes, waxes, adhesives and fillers, etc.

Fiber materials can be, for example, as endless threads. Staple fibers. Flakes. Strand goods, textile Threads. Yarn. Twists, nonwovens. Felts. Wadding. Flocking structures or as textile fabrics or textile composites. Knitted fabrics as well as papers and cardboards or paper pulps etc. are available.

The compounds to be used according to the invention are of particular importance to the treatment from textile organic materials, in particular textile fabrics. Unless fibers, which as staple fibers or endless lasers, in the form of strands, fabrics. Knitted. Fleece, flocked substrates or composites can be present that are optically brightened according to the invention, this is done with

Advantage in an aqueous medium, in which the compounds in question in finely divided form (suspensions, if necessary, solutions) are available. If necessary, dispersants can be added during the treatment become, such as B. Soaps, polyglycol ethers of fatty alcohols, Fetiamines or alkylphenols, cellulose sulphite waste liquor or condensation products of optionally alkylated naphthalenesulfonic acids with Formaldehyde. It proves to be particularly useful in neutral, weakly alkaline or acidic Bath to work. It is also advantageous if the treatment at elevated temperatures of about 50 to 100 C, for example at the boiling point of the bath or in its vicinity (about 90 C). For the Finishing according to the invention can also be used in solutions in organic solvents.

The novel optical brightening agents to be used according to the invention can also be added to the materials be added or incorporated before or during their deformation. So you can, for example in the production of films. Sheets, tapes or moldings of the molding compound or injection molding compound add or dissolve, disperse or otherwise finely distribute in the spinning mass before spinning. The optical healers can also be the starting substances, reaction mixtures or intermediate products for the production of fully or semi-synthetic organic materials are added, so too before or during the chemical reaction, for example in the case of a polycondensation (i.e. also Precondensates), in the case of a polymerization (including prepolymers) or a polyaddition.

The new optical brighteners can of course also be used wherever organic materials of the type indicated above with inorganic materials in any form can be combined (typical examples: detergents, white pigments in organic substances).

The new optically brightening substances are characterized by particularly good hit / e resistance, Lightfastness and migration resistance.

The amount of the new optical brighteners to be used according to the invention, based on the optical material to be lightened can vary within wide limits. Even with very small quantities, in In certain cases, e.g. those of 0.001 percent by weight, a clearer and more durable effect can be achieved will. However, amounts of up to about 0.5 percent by weight and more can also be used. For most practical purposes, amounts between 0.01 and 0.2 percent by weight are preferred of interest.

The new compounds used as lightening agents can also be used, for example, as follows:

a) As a mixture with dyes or pigments or as an addition to dye baths. Pressure-. Etching or reserve pastes. Also for post-treatment of dyeings. Printing or Ät / -drucken.

b) In mixtures with so-called "carriers", antioxidants, light protection agents, hit / estabilizers, chemical bleaches or as an additive to bleach baths.

c) In a mixture with crosslinkers. Finishing agents such as starch or synthetically accessible finishes. The products according to the invention can advantageously also have a wrinkle-proof coating Equipment used in the fleet can be added.

d) In combination with detergents. The washing center) and brightening agents can be used Wash baths are added separately. It's beneficial too. To use detergent, which contain the whitening agents mixed in. Soaps, for example, are suitable as detergents. Sulphonate detergent salts, such as B. of sulfonated on the 2-carbon atom by higher Alkyl radicals substituted benzimidazoles, also salts of monocarboxylic acid esters of 4-sulfophtha.'säuremit higher fatty alcohols, also salts of fatty alcohol sulfonates, alkylarylsulfonic acids or condensation products from higher fatty acids with aliphatic oxy- or aminosulfonic acids. Furthermore, non-ionic Detergents are used, e.g. B. polyglycol ethers, which differ from ethylene oxide and higher fatty alcohols. Derive alkylphenols or fatty amines.

e) In combination with polymeric carrier materials (polymerization, polycondensation or polyaddition products), in which the brighteners possibly stored alongside other substances in dissolved or dispersed form are. z. B. for coating, impregnating or binding agents (solutions, dispersions, emulsions) for textiles. Fleece, paper, leather.

f) As additions to a wide variety of industrial products in order to make them more marketable or avoid disadvantages in usability / u, z. B. as additives / u glues, adhesives, paints, etc.

The treatment of polyester fibers or polyamide fibers with the brighteners according to the invention can e.g. B. also consist in the fact that these fibers with the aqueous dispersions of the lightening agent Temperatures below 75 C, e.g. B. at room temperature, impregnated and a dry heat treatment at temperatures above KK) C, it is generally advisable to use the fiber material beforehand at a moderately elevated temperature, e.g. B. at at least 60 to about KX) C. to dry. the Heat treatment in the dry state is then advantageously carried out at temperatures between 120 and C. for example by heating in a drying chamber. by ironing in the specified temperature range or by treatment with dry, superheated steam. The drying and dry heat treatment can also be carried out immediately one after the other or in a single Operation to be merged.

The use of compounds of the formulas 20 and 21 is of particular application importance for the lightening of synthetic polyamides (poly-hexamelhylenediamine adipate type, polycaprolactam type) out of the spinning mass, while brighteners of the type of formulas 20 and 22 for the Lightening of polyamide fibers by normal treatment of the fibers using the exhaust or impregnation process are important.

The compounds of the formula given at the beginning can be used as Scmtillatoiren, for various Purposes of the pholographic kind, as for the electropholographic Reproduction or for supersensitivisicrimg use.

If the whitening process is combined with other treatment or refinement melhodes, it takes place the combined treatment is advantageous with the help of appropriate permanent preparations. Such preparations are characterized in that they are optically brightening compounds of the initially specified

general formula such as dispersants, detergents, carriers, dyes, pigments or finishing agents contain.

Examples 1 to 14 below illustrate the preparation of stilbenyl-1,3,4-oxdiazoles which can be used according to the invention described.

example 31.6 g of 4'-carbethoxy-stiIben-4-carboxylic acid chloride of the formula

H ₅ C ₂ O

Cl

(36)

19.3 g of p-tert-butyl-benzoesäurihydrazid and 16 g of pyridine are heated in 500 ml of dry o-dichlorobenzene in the course of 40 minutes with stirring at 100 to 110 C, stirred for 1 V ₂ hours at this temperature and then in the course of 30 minutes heated to 165 C. 24 g of thionyl chloride are added dropwise to the almost colorless suspension at 165 ° C. in 15 minutes with vigorous stirring. The now yellow reaction product is stirred for a further 5 minutes at this temperature and then cooled to about 15 ° C., 500 ml of methanol are added and the precipitated 2- [4 "-Carbäthoxystilbenyl- (4 ')] - 5- [4 '"-tert.-butyl-phenyl- (l'")] - !, 3,4-oxdiazole of the formula

H, QO

(37)

After washing with methanol and drying, about 25.1 g, corresponding to 55.5% of theory, of a pale yellow, fine-crystalline powder which melts at 198 to 199.5 ° C. Recrystallization three times from tetrachlorethylene with the help of fuller's earth results in pale yellow, very fine needles from melting point 200.5 to 201.5 C.

Analysis: C ₂₉ H ₂₈ O ₃ N ₂ (452.53).

Calculated ... C 76.97, H 6.24. N 6.19;
found .... C 76.67, H 6.20, N 6.10.

The 4-carbethoxystilbene-4-carboxylic acid chloride used as the starting material formula 36 can be produced as follows:

324 g of stilbene-4,4'-dicarboxylic acid diethyl ester will be

H ₅ C ₂ O

dissolved in 1000 ml of ethanol and 400 ml of dioxane, and 100 ml of 10 N sodium hydroxide solution were added to ^{the solution at 40 ° C.} After stirring at 40 ⁰ C, the resulting thick, cream-colored paste is cooled to about 20 C, filtered off under suction washed with dioxane and well squeezed. The moist suction filter is stirred in 10,000 ml of 5% hydrochloric acid for 2 hours, suction filtered and washed neutral with water. The raw suction filter is then stirred in 2000 ml of 1 N aqueous triethanolamine solution for 60 minutes and undissolved material is removed by filtration. The filtrate is acidified with concentrated hydrochloric acid, the resulting precipitate is suction filtered, washed neutral and dried. About 231 g of 4'-carbethoxy-stilbene-4-carboxylic acid of the formula are obtained

CH = CH

OH

(38)

as a colorless powder, the melting point of which (230 to 300 C) depends strongly on the heating rate.

Analysis: C ₁₈ H ₁₆ O ₄ (296.31).

Calculated ... C 72.96, H 5.44. O 21.60:

rounded .... C 72.75. H 5.40. O 21.34.

Boiling in excess thionyl chloride for three hours gives the just described Acid in a yield of 97% of theory, the 4'-carbethoxy-stilbene-4-carboxylic acid chloride Formula 36.

Colorless crystals of trichlorethylene from Melting point 134 to 136 C.

Analysis: C _1H H ₁₅ O, CI (314.77).

Calculated ... C 68.68, H 4.80, Cl 11.26:
found .... C 68.28, H 4.83, Cl 11.54.

1 594

If, in this example, 21.2 g of diphenyl-4-carboxylic acid hydrazide are used instead of 19.3 g of p-tert-butylbenzoic acid hydrazide, then about

37.8 g corresponding to 80.2% of theory 2- [4 "-carbai oxy-stilbenyl- (4 ')] - 5- [4' "- biphenylyI- (1" ')] - 1,3,4-c diazole of the formula

H ₅ C ₂ O

CH = CH

Very fine crystals of o-dichlorobenzene with a pale green tint. Melting point: 269.5 to 270.5 C.

Analysis: C ₃₁ H ₂₄ O ₃ N ₂ (472.52). Calculated ... C 78.79, H 5.12, N 5.93; Found C 78.72, H 5.14, N 6.16.

The following stilbenyl-1,3,4-oxdiazole derivatives can be prepared in a similar manner: 2- [4 "-Carbethoxy-stilbenyl- (4 ')] -5-phenyl-1,3,4-oxdiazole of the formula

H ₅ C ₂ O

I = CH

Yield: 59.1% of theory. Light yellow, finely crystalline powder from dioxane-ethanol.

Melting point: 180.5 to 181.5 C.

Analysis: C ₂₅ H ₂₀ O ₃ N ₂ (396.43). Calculated ... C 75.74, H 5.09, N 7.07: found .... C 75.44, H 5.26, N 7.14.

2- [stilbenyl- (4 ')] - 5- [naphthyl- (2 ")] - 1,3,4-oxdiazole of the formula

Analysis: C ₂₁₁ H ₁₈ ON ₂ (374.42).

Calculated ... C 83.40, H 4.85, N 7.48; found .... C 83.21. H 4.90, N 7.35.

2 - [stilbenyl - (4)] - 5 - [4 "- methyl - phenyl ■■ (! T 1,3,4-oxdiazole of the formula

CH = CH

CH = CH

N—

-N

(41)

Yield: 74.5% of theory. Pale yellow, shiny flakes of o-dichlorobenzene.
Melting point: 199 to 199.5 C. Yield: 83.7% of theory.

Almost colorless, very fine needles made of Tetn chloroethylene.

Melting point: 193.5 to 194.5'C.

Analysis: C ₂₃ H ₁₈ ON ₂ (338.39).

Calculated ... C 81.63, H 5.36, N 8.28; found .... C 81.53, H 5.10, N 8.55.

2- [stilbenyl- (4 ')] - 5- [4 "-biphenylyl- (1")] - 1,3,4-0) diazole of the formula

CH = CH

Yield: 87.5% of theory. Colorless nodules and leaves made of tetrachlorethylene.

Melting point: 227 to 228 C.

Analysis: C ₂₈
Calculated .
found .

H ₂₀ ON ₂ (400.46). . C 83.97. H 5.03. N 7.00:. C 84.15. H 5.11. N 6.90.

Example 2

8.91 g of 4- [2 '- (4 "-Biphenylyl- (1")] - l \ 3 \ 4'-oxdiazolyl (5)] Benzoic acid hydrazide of the formula

Η, Ν-ΝΗ

7.9 g of 4'-carbethoxy-stilbene-4-carboxylic acid chloride of the formula 36 and 8 g of pyridine are dried in 200 ml

Heated o-dichlorobenzene to 100 to 110 ° C. in the course of 30 minutes with stirring, for 1 hour at this Stirred temperature and then heated to 160 to 165 ° C in the course of 15 to 30 minutes. Room the colorless suspension are at 160 to 165 ° (in 15 minutes 12 g of thionyl chloride under vigorous Stir added dropwise. The yellow reaction product is stirred for a further 5 minutes at this temperature cools to about 20 ° C., sucks off, washes with methano and dries. About 12.9 g are obtained, corresponding 83.9% of theory of the 1,3,4-oxdiazole derivative de formula

H ₅ C ₂ O

CH = CH

in the form of a pale yellow powder which melts at 326 to 327 ° C. After recrystallizing twice from trichlorobenzene with the help of fuller's earth pale yellow, very fine crystals of Melting point 337.5 to 339 "C obtained.

Analysis: C ₃₉ H ₂₈ O ₄ N ₄ (616.65).

Calculated ... C 75.96, H 4.58, N 9.09;
found .... C 75.87. H 4.59, N 9.22.

The 4- [2 '- (4 "-Biphenylyl- (1")] used as starting material -1 ', 3', 4'-oxdiazoly! - (5 ')] -benzoic acid hydrazide of Formula 44 can be prepared as follows will:

106.1 g of diphenyl-4-carboxylic acid hydrazide, 93.5 g of terephthalic acid monomethyl ester chloride and 80 g of pyridine are ^{heated to 100 to 110 °} C. in the course of 40 minutes in 800 ml of dry o-dichlorobenzene, for 1 hour Stirred temperature and then heated to 160 to 165 ° C in the course of 30 minutes. 70 g of thionyl chloride are added dropwise to the colorless suspension at 160 to 165 ° C. in the course of 40 minutes, with gradual dissolution. The mixture is stirred for a further 5 to 10 minutes at this temperature, cooled to about 15 ° C., the reaction product which has precipitated in crystalline form is suction filtered, washed with methanol and dried. About 157.2 g, corresponding to 88.3% of theory, of 2- [4'-biphenylyl- (1 ')] - 5- [4 "-carbomethoxyphenyI- (1")] - 1,3,4- are obtained oxdiazole of the formula

H ₃ CO

- N

(46)

in the form of an almost colorless, finely crystalline powder that melts at 217 to 218 ° C. After three times Recrystallize from o-dichlorobenzene under

CH = CH

50 55

60

With the aid of fuller's earth, colorless, very fine crystals with a melting point of 220 to 220.5 "C are produced obtain.

Analysis: C ₂₂ H ₁₆ O ₃ N ₂ (356.36).
Calculated ... C 74.14, H 4.53, N 7.86;
found .... C 74.14, H 4.55, N 8.18

To prepare the hydrazide of the formula 44, 106.9 g of methyl ester of the formula 46 are used in 1500 ml of methyl

glycol stirred with 75 g of hydrazine hydrate for 15 hours at reflux temperature, then to room temperature cooled, suction filtered, washed with methanol and dried. About 93.7 g are obtained accordingly 87.7% of the theory of 4- [2 '- (4 "-Biphenyl-

yl-d ")] - r, 3 ', 4'-oxdiazolyl- (5')] -benzoic acid hydrazide of formula 46 in the form of a colorless powder with a melting point of 337 to 338 "C.

Example 3

12.2 g stilbene-4-carboxylic acid chloride, 13.4 g 4 - [5 - methyl - benzoxazolyl - (2 ')] - benzoic acid hydrazide of the formula

45

H ₂ N-

and 10 g of pyridine are in 400 ml of dry o-dichlorobenzene heated to 100 to 110 ° C over the course of 30 minutes with a stirrer, 1 hour on diesel Stirred temperature and then heated to 165 to 170 ° C in the course of 15 to 30 minutes. To your colorless suspension of the reaction product becomes 12 g of thionyl chloride at 165 to 170 ° C in 15 minutes is added dropwise with vigorous stirring, gradually dissolving. The mixture is stirred for a further 5 minutes at this temperature, cools down to about 15 ° C the precipitated 1,3,4-oxdiazole derivative sucks there formula

washes with methanol and dries. This gives about 18.6 g, corresponding to 82% of theory of a blaßgelbea fine crystalline powder which melts at 333 te 338 "C. After three times of recrystallization from o-dichlorobenzene

1515

25 au

With the help of Bleicheric, almost colorless, very fine noodles with a melting point of 341 to 343 C.

Analysis: C ₁₀ H ₂₁ O ₂ Nj (455.49).

Calculated ... C 79.10, H 4.65. N 9.23: found .... C 78.82. H 4.79. N 9.36.

The following 1,3,4-oxdia / ol derivatives can be prepared in a similar manner: From 15.8 g of 4'-carboethoxy-stilbene-4-carboxylic acid chloride of the formula 36 and 13.4 g of 4- [5-Meihvl-ben / oxa / olyl- (2 ')] benzoic acid hydrazide of the formula 47 the 1,3.4-Oxdia / ol derivatives of the formula

H ₅ C ₂ O

C -

CH-CH

N N

CH,

Yield: 22.3 g, corresponding to 85% of theory.
Pale greenish yellow, finely crystalline powder of o-dichlorobenzene. Melting point: 318 to 320 C.

Analysis: C ₃₃ H ₂₅ O ₄ N ₃ (527.55).

Calculated ... C 75.13, H 4.78, N 7.97; found .... C 75.08. H 4.77, N 8.26.

From 7.9 g of 4'-carbethoxy-stilbene-4-carboxylic acid chloride of the formula 36 and 7.58 g of 4- [naphth- (2: 1) -oxa?: Olyl- (2 ')] benzoic acid hydrazide the formula

O O

H, N

the 1,3,4-oxdiazole derivative of the formula

H ₅ C ₂ O

CH = CH

Yield: 9.5 g. corresponding to 67.9% of theory. Light yellow, very fine crystals of o-dichlorobenzene. Melting point: 328.5 to 329 C.

Analysis: C ₃₆ H ₂₅ O ₄ N ₃ (563.58).

Calculated ... C 76.72. H 4.47. N 7.46: found .... C 76.80, H 4.59, N 7.48.

From 6.14 g of stilbene ^ -carboxylic acid chloride and 7.58 g of 4- [naphth- (2: 1) -oxazolyl- (2 ')] -benzoic acid hydrazide Formula 50 the 1,3,4-oxdiazole derivative of the formula

-CH = CH

N N

Yield: 8.1 g, corresponding to 65.8% of theory. Light yellow, very fine crystals of o-dichlorobenzene. Melting point: 330 to 331 C.

Analysis: C ₃₃ H ₂₁ O ₂ N ₃ (491.55).

Calculated ... C 80.64, H 4.31, N 8.55: found .... C SOJO, H 4.21, N 8.49.

The 4- [naphth- ^^ iS ^ y & M <kt For- 63.6 g of 1-amino-2-oxynaphthalene and 79.5 g of methyl benzene-1-carboxylate i-carboxylic acid chloride valued the under exclusion * ^ n Air in 400 ml of anhydrous o-dichlorobenzene gradually warmed to 160 ° C. _{in the course of 3 1/2 hours.} After adding 2 g of boric acid, the temperature is increased to about 200 to 210 ° C., the o-dichlorobenzene being almost completely distilled off. During the subsequent cooling, the brown reaction solution is diluted first with 20 μl of dioxane and then with 200 μl of methanol. You cool down! "

1i515

1 594 ÖZ4

10

with cold methanol and dry. About 115.8 g are obtained, corresponding to 95.4% of the theory of 4-f N.iphth- (2: 1) -oxazolyl -12 ')] -benzoic acid-methyl ester in the form of a light, yellowish powder, which at 198 to IV C. melts. For further purification, the lister is recrystallized from Tetraehlorälhylen with the help of fuller's earth and sublimed in a high vacuum. A nearly colorless, fcinkrisiallincs powder with a melting point of 203 ° C. is obtained.

Analysis: C "H,., O., N (303.30).

Calculated ... C 75.24. H 4.32, N 4.62: found .... C 75.47, H 4.26, N 4.63.

151.5 g of the Melhy! Ester are dissolved in 750 ml of diethylene glycol diethyl ether with 50 g hydra / inhydrate 24 hours a day stirred at 110 to 115 C, then cooled, diluted with 1000 ml of methanol, suction filtered, with methanol washed and dried. About 151.2 g are obtained. corresponding to 99.8% of theory. 4-f.Naphth- (2 : l) -oxazoI> l- (2 ')] - benzocic acid hydraid of the formula 20 mel 50 in the form of a pale yellow, finely crystalline powder that melts above 4 (K) C.

The 4- [~ 5-methylbenzoxazolyl- (2 ')] benzoic acid hydrazide used as starting material can be used in an analogous manner represented by formula 47.

Almost colorless, fine noodles with a melting point of 259.5 to 260.5 C.

Example 4

15.8 g of 4'-carbethoxy-stilbene-4-carboxylic acid chloride of formula 36, 1.25 g flydrazine hydrazine hydrate and 8 g of pyridine are dissolved in 200 ml of dry o-dichlorobenzene in the course of 30 minutes with stirring 100 to I IOC heated, 1 hour at this temperature stirred and then heated to 170 ° C in the course of 15 to 30 minutes. To the almost colorless one The suspension is added dropwise at 170 ° C. in 15 minutes with 12 g of thionyl chloride while stirring vigorously. The now almost dissolved reaction product is stirred for a further 5 minutes at this temperature and cooled then to about 15 C. The 2,5 - bis - [4 "- carbethoxy - stilbenyl - (4 ')] -1.3,4 - oxdiazole which precipitated out in crystalline form the formula

H ₅ C ₂ O

I! V = / CH = CH-

OC ₂ H ₅
C (53)

Il ο

is sucked. washed with methanol and dried. About 10.2 g are obtained, corresponding to 71.6% of the Theory, pale yellow crystals melting at 330 to 332 C. After three recrystallizations o-Dichlorobenzene with the aid of fuller's earth 35 pale yellow, shiny, fine crystals with a melting point of 330 to 331 ° C. are obtained.

Analysis: C ₃₆ H ₃₀ O ₅ N ₂ (570.62)

Calculated ... C 75.77, H 5.30. N 4.91;
found .... C 75.76, H 5.48, N 5.03.

In an analogous manner, 2.5-bis- [4 "-methylslilbenyl- (4 ')] - 1,3,4-oxdiazole can be obtained from 4'-methylsilbene-4' - carboxylic acid chloride the formula

V-CH,

(54)

-N

Ν—

getting produced.
Yield: about 49.3% of theory. Pale yellow, shiny flakes of o-dichlorobenzene. Melting point: 306 to 307 C.

Analysis: C ₃₂ H ₂₆ ON ₂ (45434).
Calculated ... C 84.55, H 5.77, N 6.16: found .... C 8428, H 5.69, N 6.15.

The inquiring stilbenyl-1,3,4-oxdiazole derivatives can be represented in a similar way: 2,5-Bif> [4 "-methoxy-stiIbenyl- (4 ')] - 1,3,4-oxdiazole of the formula

H ₃ CO

CH = CH

OCH, (551

Pale yellow, shiny, matted needles and leaves made of o-dichlorobenzene. Melting point:

Analysis:

Calculated ... C 7 * 99, H 539, N 5.76; found .... C 78.91. H 5.46, N 5.85.

1515

30th

2,5-bis [4 "-chloro-stilbenyl- (4 ')] - 1,3,4-oxdiazole of the formula

V-

Cl (56)

Ii ii

N N

Pale green, shiny leaves and needles made from o-dichlorobenzene.
Melting point: 305 to 305.5 ° C.

Analysis: C ₃₀ H ₂₀ ON ₂ Cl ₂ (495.41).

Calculated ... C 72.74, H 4.07, N 5.65; found .... C 72.75, H 4.19, N 5.74.

2,5-bis- [4 "-phenyI-stilbenyl- (4 ')] - 1,3,4-oxdiazole of the formula

CH- = CH

// V CH = CH

Il

-N

Yield: 89.4% of theory.

Light yellow, shiny trichlorobenzene leaves.

Melting point: 382 to 384 "C.

Analysis: C ₄₂ H ₃₀ ON ₂ (578.68).

Calculated ... C 87.17, H 5.23, N 4.84; found .... C 87.28, H 5.25, N 4.91.

Example 5

11.9 g of stilbene-4-carboxylic acid hydrazide, 2.2 g of stilbene-carboxylic acid chloride and K) g of pyridine are heated in 200 ml of dry o-dichlorobenzene to 100 to 110 ° C. over the course of 30 minutes without stirring, 1 Stirred at this temperature for another hour and then heated to 165 to 170 ° C. over the course of 15 to 30 minutes. To the blaßgclben Suspension "12 g of thionyl chloride C in 15 minutes added dropwise arises after which a clear, yellow solution. The mixture is stirred 5 minutes at this temperature and cools it to about i5" be at 165 to 170 C from _T wherein the reaction product crystalline fails. After suction filtering, washing with methanol and drying, about 17.4 g, corresponding to 81.8% of theory, 2,5-bis- [stilbenyl- (4 ')] - 1,3,4-oxdiazole of the formula

CH = CH

Il

N-

CH = CH

pale yellow in the form of needles, melting at 278-279 ⁰ C. After three recrystallization from o-dichlorobenzene with the aid of fuller's earth, almost colorless, shiny, fine flakes with a melting point of 279 to 279.5 ° C. are obtained.

Analysis: C ₃₀ H ₂₂ ON ₂ (426.49).

Calculated ... C 84.48, H 5.20, N 6.57; found .... C 84.12, H 5.17, N 6.81.

If instead of the 12.2 g of stilbene-4-carboxylic acid chloride, 15.8 g of 4'-carbethoxy-stilbene-4-carboxylic acid chloride are used of formula 36, about 18.9 g, corresponding to 76% of the theory of 2- [4 "-carbethoxy-stiIbenyl- {4 ')] - 5- [stilbenyH4"')] - 1,3,4-oxdiazole are obtained the form!

H ₅ C ₂ O

CH = CH

which after two recrystallization from o-dichlorobenzene with the aid of fuller's earth pale yellow, very fine crystals with a melting point of 308 to 309 ° C.

Analysis: C ₃₃ H ₂₆ O ₃ N ₂ (498.55). Calculated ... C 79.50, H 5.26, N 5.62; gerand .... C 79.39, H 5.24, N 5.79.

CH = CH- <> (59)

Example 6

24.2 g of stilbene-4-carboxylic acid chloride, 5.9 g of oxalic acid dihydrazide and 16 g of pyridine are dissolved in 20 ml of dry o-dichlorobenzene in the course of 30 minutes with stirring to 100 to 1 hour, stirred for 1 hour at this temperature and then in the course heated to 165 to 170 ^° C. from 15 to 30 minutes. At 165

18 g of thionyl chloride were added dropwise up to 170 ° C. in 20 minutes. The mixture is stirred for a further 5 minutes at this temperature, the yellow suspension is then cooled to about C. The reaction product is suction filtered and washed with 32

Methanoi and dries. About 12.5 g are obtained, corresponding to 74.9% of theory.

2 - [Stilbeny] - (4 ') J - 5 - [5 "- stilbenyl -14") -1 ", 3", 4 "-oxdiazolyM2 ')] - !, 3,4-oxdiazole of the formula

CH = CH

N N

C- Il

-N

CH = CH

(60)

in the form of a pale yellow, finely crystalline powder with a melting point of 320 to 323 C. After three recrystallization o-dichlorobenzene with the aid of fuller's earth turns into very fine, pale yellow crystals obtained from melting point 331 to 332 ° C.

Analysis: C ₃₂ H ₂₂ O ₂ N ₄ (494.53).

Calculated ... C 77.71, H 4.48, N 11.33; Found C 77.66, H 4.63, N 11.18.

The following 1,3,4-oxdiazole derivatives can be prepared in a similar manner. From 31.6 g of 4'-carbethoxy-stilbene-4-carboxylic acid chloride of the formula 36 and 5.9 g of oxalic acid dihydrazide 1,3,4-Oxdiazoi derivative of the formula

H ₅ C ₁ O

C / VcH = CH- / Vc

N-

C-C

- N N -cH = CH

-N

OC ₂ H ₅ C (61) O

Yield: 25.9 g, corresponding to 81.3% of theory. Pale yellow, finely crystalline powder from o-dichlorobenzene. Melting point: 351 to 352 C.

Analysis: C ₃₈ H ₁₀ O ₀ N ₄ (638.65).

Calculated ... C 71.46, H 4.73, N 8.77; found .... C 71.43, H 4.68. N 8.77.

From 15.8 g of 4'-carbethoxy-stilbene-4-carboxylic acid chloride and 5.0 g of thiophene-2,5-dicarboxylic acid dihydrazide 1,3,4-oxdiazole derivative of the formula

OC ₂ H ₅

OC ₂ H ₅

(62)

Yield: 14 g, corresponding to 77.9% of theory. Light yellow, very fine crystals of o-dichlorobenzene. Melting point: 371 to 372 C.

Analysis: C ₄₂ H ₁₂ O ₆ N ₄ S (720.80). Calculated ... C 69.99, H 4.48, N 7.77: found .... C 69.87. H 4.64. N 7.71.

il

From 12.2 g of stilbene-1-carboric acid chloride and 5.0 g of thiophene-2,5-dioirboxylic acid dih> dra ^ ic ⁾ the 1,3,4-oxdiazole derivative of the formula

/ V- CH = (

■ ^ j- *

HC

, I!

-CH

il

C C

N N

N - CH-CH

(63)

Yield: 10 g, corresponding to 69.6% of theory. Pale yellow, very fine, matted crystals of trichlorobenzene.
Melting point: 349 to 350 C.

Analysis: C ₃₆ H ₂₄ O ₂ N _-1 S (576.68).

Calculated ... C 74.98, H 4.20, N 9.72: found .... C 74.96. H 4.30, N 9.80.

Example 7

II.9g stilbeii-4-carboxylic acid hydrazide, 8.3 g cinnamic acid chloride and 8 g pyriclin are in 250 ml ίο dry o-dichlorobenzene in the course of 20 minutes th heated to 100 to 110 C with stirring, 1 hour stirred at this temperature and then to 165 to 170 ° C. over the course of 15 to 30 minutes heated. At 165 bi; 170 C in 15 minutes 12 g of thionyl chloride under vigorous Stir added dropwise. The now yellow solution is stirred for a further 5 minutes at this temperature, then cools down to about 5 ° C. and adds 200 ml of methanol during the cooling process. Das2- [StilbenyI- (4 ')> 5-styryl] -1,3,4-oxdiazole of the formula

A-r »=

CH = CH -

CH = CH

(64)

N N

is suction filtered, washed with methanol and dried. Analysis: C ₂₄ H ₁₈ ON ₂ (350.40). net. About 10 g is obtained. corresponding to 57.8% of the

Theory, a pale yellow powder that calculates at 186.5 to

Melts 187.5 C. Found by concentrating the mother liquor

can add a further 3.6 g with a melting point of 182 to 183 ° C be won. After recrystallizing twice from tetrachlorethylene with the aid of Colorless, fine crystals with a melting point of 187.5 to 188 ° C. are obtained.

C 82.26. H 5.18, N 8.00:
C 82.25, H 5.31, N 7.77.

The following stilbenyl-1,3,4-oxdiazole-Derivalc can be represented in a similar way:

2 - [stilbenyl - (4 ')] -5 - [p-methyl-styryl] -1,3,4-oxdi;: zol the formula

V-CH-CH

C C

Il Il

N N

CH = ■ ---- CH

-CH,

(65)

Yield: 74.6% of theory.

Pale yellow, finely crystalline powder made from telrachlorethylene.

Melting point: 203.5 to 204 C.

Analysis: C ₂₅ H ₂₀ ON ₂ (364.43).

Calculated ... C 82.39. H 5.53, N 7.69; found .... C 82.23, H 5.55, N 7.54.

2-fStilbenyl- (4 ')] -5-fp-melhoxy-styryI] -1, 3,4-oxdiazole of the formula

CH --- CH

N-

CCH =

Il

(66)

Yield: 52.2% of theory.

Pale yellow cs. finely crystalline powder of trachlorethylene.

Melting point: 194 to 194.5 C.

Analysis: C ₂₅ H _2n O ₂ N, (380.43).
Calculated ... C 78.92. H 5.3 (1 '. N 7.36: found C 78.96, 115.45. N 7.19.

Il

2-l'S'liIbenyl- (4 ')] -5-fn-pheny! -Styr> l] -l, 3,4-oxdiazole of the formula

CH-CH

Light yellow flakes of chlorobenz / o! Melting point: 262 to 263 C.

Analysis: C ₃₀ H ₂₂ ON, (426.49).

Calculated ... C 84.48, H 5.20, N 6.57; found .... C 84.38, H 5.31. N 6.83.

Example 8

11.91 g of stilbene-4-carboxylic acid p-hydrazide, 11.17 g S-phenyl-thiophene ^ -carboxylic acid chloride and 8 g of pyridine are in 200 ml of dry o-Dichlorbenzoi im

= CH

in the form of a pale yellow powder which melts at 270.degree. Recrystallization three times from tetrachlorethylene results in pale greenish yellow, fine, matted Needles with a melting point of 270 C.

Analysis: C ₂₀ H ₁₈ ON ₂ S (406.51).

Calculated ... C 76.82, H 4.46, N 6.89: found .... C 76.39. H 4.50, N 6.84.

The following 1,3,4-oxdiazole derivatives can be prepared in a similar manner:

The course of 20 minutes was heated to 100 to 110 ° C. while stirring, and the mixture was subsequently stirred at this temperature for 1 hour and then heated to 165 to 170 ° C. in the course of 15 to 30 minutes. To the light yellow solution are at 165 to 170 C in 15 minutes 12 g of thionyl chloride added dropwise. The mixture is stirred for a further 5 minutes at this temperature and the now yellow solution is cooled of the reaction product to about 20 C. sucked the precipitated crystals, washed with methanol and dries. About 16.7 g are obtained, corresponding to 82 3% of theory. 2-fstilbenyl- (4 ')] - 5- [5 "-phenylthienyl- (2")] - 1,3,4-oxdiazole the formula

CH

C-C

CH

C- / V

N N

From 97.74 g of 4'-carbethoxy-stilbene-4-carboxylic acid halide and 65.46 g of 5-phenyl-thiophene-2-carboxylic acid hydrazide (prepared by refluxing 1 mole of 5-phenylthiophene-2-carboxylic acid ether with 4 moles of hydrazine hydral in ethanol ; Melting point 165.5 to 166.5 ¹ C) with 56 g of pyridiri in 1200 ml of dry o-dichlorobenzene and ring closure with 60 g of thionyl chloride 2- [4 "-Carbäthoxysiilbenyl- (4 ')] - 5- [5 '"-phynyl-thienyl- (2'")] - 1,3,4-oxdiazole of the formula

H ₅ C ₂ O

CH = CH

O CH CH

/ \ Ii Il c c ~ c c

N N 'S

Yield: 122.2 g, corresponding to 85.4% of theory. Light yellow, very fine crystals of o-dichlorobenzene. Melting point: 294.5 to 295.5 "C.

Analysis: C ₂₉ H ₂₂ O _x N ₂ S (478.57).

Calculated ... C 72.78, H 4.63, N 5.85; Found ... C 72.66, H 4.69, N 5.86.

From 23.83 g of stilbene-4-carboxylic acid hydrazide and 19.26 g of thiophene-2,5-dicarboxylic acid monomethyl ester chloride the 2- [stilbenyl- (4 ')] - 5- [5 "-carbomethoxy-thienyl- (2")] - 1.3.4-oxdiazole of the formula

CH CH

f V-CH = CH-T V-C

OCH.,

N N

Bulge: 31.0g, corresponding to 82.0% of theory. Light yellow, very fine crystals of o-dichloromine / oil. Melting point: 227.5 to 228.5 ° C

Analysis: C ₂₂ H ₁ , O _-1 N ₂ S (388.45).

Calculated ... C 68.03, H 4.15, N 7.21: found .... C 68.23, H 3.93, N 7.22.

2- [stilbenyl- {4 ')] - 5- [thienyl- (2 ")] - 1,3,4-oxdiazole 2-carboxylic acid hydrazide of the formula
the formula

O CH CH O

O CH CH%. 11 Κ / ^x

J ~ K S ~ \ / \ Il Il 5 cc cc c

" ^ -CH = CH ~ f Vc CC CH / \ / I! !!

^{X = /} II II \ / H ₁ N-NH SNN

NNS _{(71 |}

Yield: 333% of theory
Almost colorless, matted needles made of dioxane, ethanol - water.

Melting point: 174 to 174.5 C. ^J

Analysis: C ₂₀ H ₁₄ ON ₂ S (330.41).

Calculated ... C 72.70, H 4.27. N 8.48; found C 7Z53, H 4.47. N 8.62.

Example) 9

6.14 g stilbene-4-carboxylic acid chloride. 7.16 s 5- [5'-phenyl- (r ') - r, 3'.4'-oxdiazolyl- (2')] - thiopheif-ίο (prepared from 5 - [5 '- phenyl - (I " ) - Γ, 3 ', 4' - οχ diazolyl - (2 ')] - thiophene - 2 - carboxylic acid methyl ester and hydrazine hydrate in the warm; melting points 228 to 229.5 Cl and 8 g of pyridine are in 200 m dry o-dichlorobenzene im The mixture is heated to 100 to 110 ° C. in the course of 20 minutes with stirring, stirred at this temperature for 1 hour and then heated in the course of 15 to 30 minutes to 165 to 170 ° C. The pale yellow suspension of the reaction product is added at 165 to 170 ° C. in 15 minutes 10 g of thionyl chloride are added with vigorous stirring, the solution gradually falling in. The mixture is stirred for a further 5 minutes at this temperature, then cooled to about 15 ° C. and 2 (X) ml of methanol are added -Derivative of the formula

O CH CH O

'\ il Il / \

N-

N N

is sucked, washed with methanol and rocked. About 7.5 g, corresponding to 63.2% of theory, of a light yellow powder are obtained, which is 293 to C melts. Recrystallization three times from o-dichlorobenzene with the aid of fuller's earth results in light yellow, fine crystals with a melting point of up to 299 "C.

CH = ^ CH

Aiuilyse: C ₂₈ H ₁₈ O ₂ N ₄ S (474.54).

Calculated ... C 70.87, H 3.32, N 11.81;
found .... C 70.69. H 4.03, N 11.71.

The following 1,3,4-oxdiazole derivatives can be prepared in an analogous manner:

CH CH

C-C

N-

-N CC

N-

-N

Yield: 10.5 g, corresponding to 83.4% of theory. Light yellow, fine needles. o-dichlorobenzene. Melting point: 305 to 306 ° C

Analysis: C ₂₉ H ₂₀ O ₃ N ₄ S (504.57).

Calculated ... C 69.03, H 4.00, N 11.10: Found ... C 68.84, H 4.18, N 11.07.

H ₅ C ₂ O

= CH

Yield: 12.8 g, corresponding to 85.2% of theory. Light yellow, fcine-crystalline powder made from o-dichlorobenzene. Melting point: 313 to 314 C.

Analysis: C '"II ₁₁₁ O ₄ N ₄ S (602.71).
Hcrcchnct ... C 69.75. 115.02, N 9.30; ... C 6tf, 68. H 5.12. N 9'.SN.

C-
Il CH
Η S. -CH
I. CH ₃ (75) /
C. Il
-N Il
C.
\ I /
CC > - C- CH ₃ N- \ N- CH ₃ O
/ \ O
/ \ Il
-N

Example 10

5.96 g of stilbene-4-carboxylic acid hydrazide. 6.6µ 5 - [Benzoxazolyl- (2) j-thiophen-2-curbonic acid chloride the formula

CH CH O ⁵ '

Cl

/ · ■■

c-c

C C

(76)

and 8 g of pyridine are heated in 250 ml of dry o-dichlorobenzene over the course of 20 minutes with a stirrer to KX) to IK) C, stirred at this temperature for 1 hour and then heated to 165 to 170 ° C. over the course of 15 to 30 minutes. To the colorless suspension of the reaction product, 12 g of thionyl chloride are added dropwise at 165 to 170 ° C. in 15 minutes with vigorous stirring, a yellow, clear solution gradually forming and adds 200 m of methanol.
The 1,3,4-oxdiazole derivative of the formula

/ V-CH =

CH- <f V-C C-C

\ = y ii i!

N N S N

is suction filtered, washed with methanol and dried. About 8.3 g are obtained, corresponding to 74.3% of theory a light yellow powder that melts at 285 to 286 C. By concentrating the mother liquor, a further 2 j with a melting point of 279 to 284 "C. Recrystallization three times from o-dichlorobenzene results fine, matted, light yellow noodles with a melting point of 288 to 289 C.

Analysis: C ₂₇ H ₁₇ O ₂ N ₃ S (447.52).

Calculated ... C 72.47. H 3.83, N 9.39; found ... C 72.27. H 3.75, N 9.44.

The 1,3,4-oxdiazole derivative of the formula

O CH CH

'\ il Il

CH = - CH

Il

N-

CH ₃

C - C

I!

c-c

/ \ ν CCH 3

CH ₃

getting produced.

Yield: 5.7 g. corresponding to 45.3% of theory. Light yellow, fine noodles made of tetrachlorethylene. Melting point: 287 to 288.5 "C.

Analysis: C ₃₁ H ₂₅ O ₂ N ₁ S (503.62).

Calculated ... C 73.93, H 5.00. N 8.34: found .... C 74.07, H 5.08, N 8.54.

The 5- [benzoxazolyl- (2 ')] -lhiophene-2-carboxylic acid chloride used as the starting material formula 76 can be made as follows:

579 g of 5- [benzoxazolyl- (2 ')] -thiophene-2-carboxylic acid are refluxed in 35 (K) ml of chlorobenzene with 250 ml of thionyl chloride with the addition of 10 ml of dimethyl formamide for 2 hours. Then mm adds another 250 ml of thionyl chloride and refluxes for a further 2 hours. Now the excess thionyl chloride is distilled off with about half of the solvent, the distillation residue is filtered hot and allowed to cool. The 5- [benzoxazolyl- (2 ')] -thiophene-2-carboxylic acid chloride of the formula 76 crystallizes out. After suction filtering, washing with n-hexane and drying, 530 g, corresponding to 83.8% of theory, biaßgeibe crystals with a melting point of 163 to 164 C are obtained, which after recrystallization from chlorobenzene give the following analytical values :

C ₁₇ H ₆ O ₂ N ₁₁ SCI (263.70).

Calculated ... C 54.66, H 2.29, Cl 13.44;
found .... C 54.36. H 2.11, Cl 13.34.

In an analogous manner, the 5- [5'-tert-butyl-benzoxazolyl- (2 ')] - thio used as the starting material phen-2-carboxylic acid chloride are produced.

Pale yellow, shiny crystals of ligroin.

Melting point: 176 to 178 ¹ C.

Analysis: C ₁₆ H ₁₄ O ₂ NSCl (319.81).

Calculated ... C 60.09, H 4.41, N 4.38, Cl 11.09; found .... C, 60.17. H 4.33. N 4.25. Cl 11.24.

Example Il

3.19 g of 4-phenyl- stilbene -4-carboxylic acid chloride 1.36 g of benzoic acid monohydrazide and 1.6 g of pyridii are heated in 100 ml of dry o-dichlorobenzene over the course of 15 minutes with stirring to 100 ° -110 ° C. for 1 hour stirred at this temperature and then heated in the course of 10 to 20 minutes to 130 to 135 ° C. 2.5 M thionyl chloride are added dropwise to the pale yellow suspension at 130 to 135 ° C. The resulting pale yellow solution is stirred at this temperature for another 30 minutes, then cool to about 5 ° C. and add 200 ml of methanol while cooling

509628/30

1515

suction filtering, washing with methanol and drying gives about 3.5 g. corresponding to 87.5% of the Theory 2 - [4 "- Phenyl - stilbenyl - (4 ')] - 5 - phenyl-1,3,4-oxdiazole of the formula

in the form of a pale yellow powder which melts at 209 to 210 C. After three recrystallizations Tetrachlorethylene with the help of fuller's earth is about 2.0 g, corresponding to 50.3% of theory, pale yellow, shiny needles and leaflets with a melting point of 222 to 222.5 ° C. were obtained.

Analysis: C ₂₈ H ₂₀ ON ₂ (400.46).

Calculated ... C 83.97, H 5.03, N 7, (X); Found ... C 84.01, H 5.19, N 6.84.

The following stilbenyl-1,3,4-oxdiazole derivatives can be prepared in a similar manner: 2- [4 "-Phenyl-stilbenyl- (4 ^/ )] - 5-f4 '" - tert-butylphenyl- (r " )] - 1,3,4-oxdiazole of the formula

N N

Yield: 78.9% of theory.

Pale green, shiny needles made of tetrachlorethylene.

Melting point: 239 to 239.5 ° C.

Analysis: C ₃₂ H ₂₈ ON ₂ (456.56).

Calculated ... C 84.18, H 6.18, N 6.14; Found ... C 84.36, H 6.28, N 5.94.

2- [4 "-Phenyl-stilbenyl- (4 ')] - 5" [4 "' - biphenylyl- (i '")] - !, 3,4-oxdiazole of the formula

CH ₃

CH ₃

CH = CH

Yield: 83.9% of theory.

Pale yellow, shiny flakes of o-dichlorobenzene.

Melting point: 282 to 283 "C.

Analysis: C ₃₄ H ₂₄ ON ₂ (476.55).

Calculated ... C 85.69. H 5.08, N 5.88; Found ... C 85.93, H 5.38, N 5.65.

2- [4 "-Phenyl-stilbenyl- (4 ')] - 5- [stilbenyl- (4"')] - 1,3,4-oxdiazole of the formula

CH = CH

CH = CH

Yield: 73.7% of theory.

Pale greenish yellow, shiny leaves and needles made from o-dichiorobenzene.

Melting point: 304 to 305 "C.

Analysis: C _3ft H _2h ON ₂ (502.58).

Calculated ... C 86.03, H 5.21, N 5.57; found ... C 85.85, H 5.41, N 5.40.

-1: 515

43

2- [4 "-Phenyl-stilbenyl- (4 ')] - 5- [4"' -methylphenyl- (1 '")] - 1,3,4-oxdiazole of the formula

«■ V /

<X

-CH = CH-

CH ₁

N -

Yield: 82.7% of theory.

Pale green, shiny tinsel made from o-dichlorobenzene.

Melting point: 239 to 239.5 C.

Analysis: C ₂₉ H ₂₂ ON ₂ (414.48).

Calculated ... C 84.03, H 5.35, N 6.76; Found ... C 83.82, H 5.47, N 6.83.

2- [4 "-Phenyl-stilbenyl- (4 ')] - 5- [4"' - niethoxyphenyl- (1 '")] - !, 3,4-oxdiazole of the formula

CH = CH

OCH.,

Bulge: 83.6% of theory.

Pale green, shiny leaves and needles made from o-dichlorobenzene.

Melting point: 225.5 to 227 "C.

Analysis: C ₂₉ H ₂₂ O ₂ N ₂ (430.48).

Calculated ... C 80.90, H 5.15, N 6.51; Found ... C 80.61, H 5.23, N 6.33.

2- [4 "-phenyl-stilbenyl- (4 ')] - 5- [2'" - melhoxyphenyl- (1 '")] - 1,3,4-oxdiazole of the formula

OCH ₁

CFJ = CH

Yield: 55.8% of theory.

Pale yellow, fine tetrachlorethylene needles.

Melting point: 194.5 to 195 "C.

Analysis: C ₂₉ H ₂₂ O ₂ N ₂ (430.48).

Calculated ... C 80.90, H 5.15, N 6.51; Found ... C 80.77, H 5.21, N 6.57.

2- [4 "-phenyl-stilbeny] - (4 ')] - 5- [3" \ 4 "' - di-rhoxyphenyl- (1 '")] - 1,3,4-oxdiazole of the formula

_o OCH ₃

N—

Yield: 51% of theory.

Light yellow, matted needles made of tetrachlorethylene.

Melting point: 228 to 229'C.

Analysis: C ₃₀ H ₂₄ O ₃ N ₂ (460.51). Calculated ... C 78.24, H 5.25, N 6.08; found ... CTJO, H5.28, N 6.17.

2- [4 "-PhenyI-stilbenyl- (4 ')] - 5- [naphthy] - (2'")] - _{1,3,4 l} -oxdiazole of the formula

Yield: 88.8% of theory.

45 'ίο

Pale greenish yellow, shiny leaves and needles made of o-dichlorobenzene. Melting point: 265 to 265.5 "C.

Analysis: C ₃₂ H ₂₂ ON ₂ (450.51).

Calculated ... C 85.31, H 4.92, N 6.22: found ... C 85.05, H 5.04. N 6.27.

2- [4 "-Phenyl-stilbeny! - (4 ')] - 5- [thicnyl- (2 ^/ ")] - 1,3,4-oxdia / ol of the formula

C H-CH- /

Yield: 85.0% of theory.

Pale greenish yellow matted tetrachlorethylene leaves.

Melting point: 219 to 219.5 "C.

Analysis: C ₂₁₅ H ₁₈ ON ₂ S (406.51).

Calculated ... C 76.82, H 4.46, N 6.89; Found ... C 76.74, H 4.45, N 6.95.

2- [4 "-phenyl-stilbenyl- (4 ')] - 5- [5'" -phenylthieny] - (2 '")] - 1,3,4-oxdiazole of the formula

O C.
Il CH
j CH
Il -C
Ü Il
■ N -C
\ Il
CH N-- \ - - ζ /
S.

(SH)

= CH \ V c
- = y 'W O C-
! I CH
Μ CH /
S. CH Il
N- | l
N Ii
C. c-
/

189)

Yield: 82.9% of theory.

Light, greenish yellow, shiny flakes of o-diehlorbenzene.

Melting point: 286.5 to 287.5 ° C.

Analysis: C ₃₂ H ₂₂ ON ₂ S (482.61).

Calculated ... C 79.64. H 4.60. N 5.80: Found ... C 79.46, H 4.68. N 6.03.

2- [4 "-Phenyl-stilbenyl- (4 ')] - 5- [furyl- (2'")] - 1,3,4-oxdiazole of the formula

CH

C-C

CH

CH

(90)

N N

Yield: 69.2% of theory.

Pale yellow, fine, matted needles made of tetrachlorethylene.

Melting point: 220 to 220.5 C.

Analysis: C ₂₆ H ₁₈ O ₂ N ₂ (390.42).

Calculated ... C 79.68, H 4.65, N 7.17: Found ... C 79.61, H 4.64, N 7.21.

The stilbenyl-1,3,4-oxdiazole derivative of the formula

CH = CH

Yield: 94.7% of theory. Bteßgreenish yellow. matted noodles made of o- dichlorobenzene.

Melting point: 351 to 352 C.

Analysis: C 1 H ₂₃ O ₂ N ₃ (517.59).

Calculated ... C 81.22. H 4.48, N 8.12; found .... C 80.99, H 4.60, N 7.85

The 4-phenylitilbene-4-carboxylic acid chloride used as starting material can be added by boiling excess thionyl chloride in o-dichlorobenzene

(91)

can be prepared from 4 - phenyl-stilbene-4-carboxylic acid in practically quantitative yield (greenish-yellow crystals with a melting point of 220 to 221 ° C.).

The 4 - phenyl-stilbene-4-carboxylic acid can be obtained, for example, from 4-formyl-diphenyl and 4-carbomethoxybenzyl chloride by the method of W i 11 ig. It crystallizes from glacial acetic acid in light greenish-yellow crystals with a melting point of 312 C.

Analysis: C ₂₁ H ₁₆ O ₂ (300.34). Calculated ... C 83.98, H 5.37; found .... C 84.19, H 5.42.

1.515

1 594 ^ 24

Example 12

6.0 g of 4 '- (styryl-biphenyl) -4-carboxylic acid are stirred in 70 ml of o-dichlorobenzene with the addition of two drops of pyridine with 20 ml of thionyl chloride for 6 hours at 80 to 90 ° C., the hydrochloric acid gas escaping and one erhäk clear solution. the excess thionyl chloride is then evaporated under reduced pressure. at a temperature of 30 to 40 ⁰ C., then 4.8 g Stilbcn- ^ carboxylic acid hydrazide and 2 ml of anhydrous pyridine and heated to the bell yellow suspension I ¹ Z ₂ hours obtain a thick paste obtained at 130 to 135 ⁰ C., innerhalh 20 minutes then added dropwise evenly SmI thionyl chloride at this temperature, with hydrochloric acid gas escapes and obtains a thin yellow suspension. the mixture is stirred then for another 20 minutes at 130 to 135 ° e , removed most of the solvent by evacuation, added alcohol and allowed to cool while stirring. The crystalline pulp is sucked off and washed with alcohol. Twice crystallization from dimethylformamide gives something a 3.1 g of the compound of the formula

CH = CH

CH = CH

(92)

N-

as light yellow leaflets with a melting point of 306 to 307 C.

Analysis: C ₃₆ H ₂₆ ON ₂ (502.58).

Calculated ... C 86.03, H 5.21, N 5.57;
Found ... C 85.76, H 5.45, N 5.63.

The following oxdiazole compounds can be prepared in an analogous manner:

/ A-CH = CH- / YV

(93)

Pale yellow crystal powder from chlorobenzene with a melting point of 285 to 287 "C.

Analysis: C ₃₄ H ₂₄ ON ₂ (476.55).

Calculated ... C 85.69, H 5.08, N 5.88;
Found ... C 85.43, H 4.97, N 5.72.

(94)

Pale yellow fine crystalline powder from dimethylformamide the melting point of 258-260 ⁰ C.

Analysis: C ₂₉ H ₂₂ ON ₂ (414.48).

Calculated ... C 84.03, H 5.35, N 6.76;
Found ... C 83.71, H 5.32, N 6.89.

CH = CH

Pale yellow flakes made of dimethylformamide with a melting point of 232 to 234 ° C.

Analysis: C ₂₈ H ₂₀ ON ₂ (400.46).

Calculated ... C 83.97, H 5.03, N 7.00;
found .... C 83.68, H 5.16, N 7.06.

The 4 '- (StyryI-biphenyl) -4-carboxylic acid used as starting material can be made as follows:

213 g of 4'-amino-diphenyl-4-carboxylic acid are with 500 g glacial acetic acid, 220 g conc. Hydrochloric acid, 400 g of ice and 300 ml of water were stirred. Within 8 hours will be $ 6 now 70 g of sodium nitrite dissolved in 140 ml of water are added dropwise, the temperature of the reaction mixture is kept at 0 to 5 ° C by ice cooling.

(95)

Then the thick liquid crystal pulp becomes with this Stirred temperature overnight. A cooled solution of 148 g of cinnamic acid is then added all at once in 1800 ml of acetone with thorough stirring and the suspension obtained is by adding about 130 ml sodium hydroxide solution to a pH of 3.0 to 3.5. Then give within 5 to 6 hours 90 to 100 g of an equimolar in portions at 0 to 5 ° C Mixture of copper and copper (II) chloride, after which the evolution of gas has ended. Man now allows the temperature of the reaction mixture to rise to 20 ° C and then distilled the acetone with steam. Then add about 600 ml of concentrated ammonia solution in the heat, lets cool while stirring, sucks and washes

with water. The residue is then mixed with 3000 ml of water at boiling temperature and added concentrated hydrochloric acid until the reaction is strongly Congo acidic. You suck and wash with hot water Water after. After drying, 119 g of a brown-beige powder are obtained, which in a high boiling point Dioxane is dissolved. After the undissolved residue has been filtered off, it is concentrated and cooled calmly.

55 g of light brown, crystalline powder, which melts indistinctly between 315 and 325 ° C., are obtained. Twice further crystallization from dioxane with the addition of activated charcoal yields the 4 '- (StyryI-biphenyI) -4-carboxylic acid as pale beige flakes with a melting point of 328 to 329 ¹ C.

Sublimation in a high vacuum gives a colorless powder with the same melting point

Analysis: C ₂₁ H ₁₆ O ₂ (300.34).

Calculated ... C 83.98. H 5.37. O 10.65:

found .... C 83.99. H 5.30. O 10.82.

Example 13
2.92 g of the acid chloride of the formula

COCl

(96)

1.92 g of 4-t-butyl benzhydrazide and 1.6 g of pyridine become in 100 ml of dry o-dichlorobenzene in the course heated to 130 ° C. for 35 minutes with stirring. Now one drips to the light yellow solution inside 2.5 ml of thionyl chloride in 25 minutes, then heated to 145 C within 30 minutes, if the solution is concentrated in vacuo to 20 ml, the crystals formed on cooling are slurried in 30 ml Methanol, suction filtered, washed with methanol and dried. About 3.4 g are obtained, corresponding to 79.5% the theory of the compound of the formula

CH = <

N-

-N

CH ₃

CH ₃

(97)

in the form of a beige powder that melts at 157 to 159 ° C. After twice recrystallizing from tetrachlorethylene with the aid of bleaching earth about 1.3 g (corresponding to 30% of theory) are colorless, shiny flakes obtained of melting point 169.3 to 169.7 C ^1.

Analysis: C ₃₀ H ₂₆ ON ₂ (430.52).

Calculated ... C 83.69, H 6.09. N 6.51;
found ... C 83.60. H 6.13. N 6.34.

In a similar way, the compound can have the formula

-CH = CH- / V-

V / \

(98)

N N

getting produced.

Yield: 54% of theory.

Light, green-tinged, fine noodles made of tetrachlorethylene.

Melting point: 211.0 to 211.3 C.

Analysis: C ₃₂ H ₁₁ ON ₂ · ¹ A _n mol of tetrachlorethylene
(458.82).

Calculated ... C 84.02, H 4.83. N 6.11, Cl 1.55;
found .... C 83.71, H 4.90, N 6.01, Cl 1.99.

The acid chloride used as the starting material can be obtained from the corresponding carboxylic acid according to Wit tig's method from I-naphlhaldehyde and 4-Carbomethoxyben7.ylchlorid can be obtained by boiling in o-Dichlorbcn / ol with excess Thionyl chloride can be produced in virtually quantitative yield. I £ s crystallizes out

60 tetrachlorethylene in yellow crystals with a melting point of 108 to 109 C.

Analysis: C ₁₉ H ₁₃ OCl (292.77).

Calculated ... C 77.95, H 4.48. Cl 12.11:
found .... C 77.68. H 4.46, Cl 12.16.

Example 14
2.92 g of the acid chloride of the formula

COCl

(99)

1.92 g of 4-part bulylbenzhydrazide and 1.6 g of pyridine are mixed in 100 ml of dry o-dichlorobenzene

'Is

run heated to 135C from 20 minutes. The pale yellow suspension is then added dropwise over the course of 22 minutes 2.5 ml of thionyl chloride, the yellow solution heated within 30 minutes to 148 ° C and

V-CH = CH

then cools down to OC. After suction filtering, washing with methanol and drying, about 3.05 g, corresponding to 69.5% of theory of the compound of the formula

Il

N-

CH ₃

/ Vc-CH ₃
CH ₃

(100)

in the form of a cream-colored powder that melts at 208 to 210 C. After recrystallizing twice Tetrachlorethylene with the aid of fuller's earth is about 1.5 g, corresponding to 34.4% of theory, Pale greenish yellow, verifiable needles with a melting point of 208.2 to 208.5 ° C were obtained.

Analysis: C ₃₀ H ₂₆ ON ₂ (430.52).

Calculated ... C 83.69, H 6.09, N 6.51;
found. ... C 83.76, H 6.09, N 6.52.

Similarly, the following oxdiazoles can be made:

/ YY CH == CH- / AC ⁷ \ VNj ^ NN

Yield: 60.7% of theory.

Pale yellow, shiny flakes of o-dichlorobenzene.

Melting point: 255 to 256 ° C.

Analysis: C ₃₂ H ₂₂ ON ₂ (450.51).

// χ (101)

Calculated ..
found .. . C.
. C. 85.31,
85.25, H 4.92,
H 5.03. N 6.22;
N 6.43. / ^ A. -CH = CH - ^ ~~ ' K / Vc " ⁷ Il
N- O
/ \ \
C. ll
-N

CH = CH

(102)

Yield: 63.5% of theory.
Almost colorless, matted crystals of o-dichlorobenzene.
Melting point: 267 to 268 C.

Analysis: C ₃₄ H ₂₄ ON ₂ (476.55).

Calculated ... C 85.69, H 5.08, N 5.88:
found .... C 85.97, H 5.21, N 5.82.

The acid chloride used as the starting material can be obtained from the corresponding carboxylic acid according to the method of W i 11 i g can be obtained from 2-naphthaldehyde and 4-carbumethoxybenzyl chloride, by boiling in o-dichlorobenzene with excess thionyl chloride in practically quantitative yield getting produced.

It crystallizes from tetrachlorethylene in pale yellowish crystals with a melting point of 154 bis 156 "C.

Analysis: C ₁₉ H ₁₃ OCl (292.77).

Calculated ... C 77.95, H 4.48, Cl 12.11;
found .... C 78.08, H 4.41, Cl 12.51.

Examples 15 to 22 below explain the use according to the invention of slilbenyl-1,3,4-oxdiazoles.

Example 15

100 g of polyester granules made from terephthalic acid ethylene glycol polyester are intimately mixed with 0.05% of the compound of the formula 53 and melted at 285 ° C. with stirring. After piecing the spinning mass through conventional spinnerets and drawing, strongly lightened polyester fibers are obtained.
The compound of the formula 53 can also be added to the starting materials before or during the polycondensation to give the polyester.

Good lightening effects are also achieved if, instead of the compound of the formula 53, the Compounds of formulas 39, 45, 49, 51, 52, 57, 59, 60, 61, 68, 73, 74, 75, 78, 79, 80, 81, 82, 87, 91, 92, 93, 95,98, 101 or 102 used.

Example 16

Bleached fabric made of polyamide staple fiber is made at a liquor ratio of 1:30 for 30 minutes treated at 90 to 95 ° C in a bath, which, based on the fiber material, 0.1% of the compound of formula 64 and 1% 40% acetic acid.

After rinsing and drying, the fabric treated in this way shows a strong lightening.

If a fabric made of polyamide filament is used instead of the fabric made of polyamide staple fiber, see above one arrives at similarly good lightening effects.

Good lightening effects are also achieved if, instead of the compound of the formula 64, one of the Compounds of the formulas 37, 40, 58, 59, 65, 66, 67, 70, 71, 79, 80, 81, 83, 84, 85, 88.97 or 100 are used.

Example 17

10,000 g of a polyamide in chip form prepared in a known manner from hexamethylenediamine adipate are mixed with 30 g of titanium dioxide (rutile modification) and 5 g of one of the compounds of the formulas 37, 39, 45, 48, 49, 51, 52, 53, 54, 56, 57 , 58, 59, 60, 61, 64, 67, 79, 80, 81, 82, 83, 84, 87, 88, 89 91, 92, 93, 94, 95, 97, 100, 101 or 102 in a roller jar mixed for 12 hours. The so-treated chips are stirred in a oil or Diphenyldampf at 300-310 ⁰ C fired boiler, after displacement of the Luftsauirstoffes melted by steam and during half an hour. The melt is then pressed out through a spinneret under a nitrogen pressure of 5 atmospheres and the cooled filament spun in this way is wound onto a spinning bobbin. The resulting threads show an excellent lightening effect of good washing and lightfastness.

If, instead of a polyamide made from hexamethylenediamine adipate, a polyamide made from t-Ca prolactam is used, similarly good results are obtained.

B e i s ρ i e 1 18

A polyester fabric is padded at room temperature (about 20 ° C.) with an aqueous dispersion containing 0.1 to 1 g of one of the oxdiazole compounds of the formulas 37, 39, 45, 49, 53, 57, 61, 80, 81, 82.91 per liter , 92,93,98,100, 101 or 102 as well as 1 g of an adduct of about 35 mol of ethylene oxide with 1 mol of octadecyl alcohol and dries at about 100 ^° C. The dry material is then subjected to ^{a heat treatment at about 220 ° C. for 30 seconds.} The polyester fabric treated in this way has a significantly higher whiteness than an untreated polyester fabric.

Example 19

40

A bleached fabric (polyamide) made of staple fibers is padded at room temperature (about 20 ° C.) with an aqueous dispersion containing 0.1 to 1 g of an oxdiazole compound of the formulas 58 or 80 and 1 g of an adduct of about 35 moles of ethylene oxide per liter 1 mol octadecyl alcohol contains and, dried at about 8O ⁰ C. The dry material is then subjected to a heat treatment at about 160 "C for 3 minutes. The polyamide fabric treated in this way has a significantly higher whiteness than an untreated polyamide fabric.

If one uses in place e ^; A fabric made of polyamide staple fibers a fabric made of polyamide filament leads to similarly good lightening effects.

Example 20

100 g of “Fiber-Grade” polypropylene are intimately mixed with 0.08 g of the compound of the formula 58 and ^{melted at 280 to 290 °} C. with stirring. The melt is spun out and drawn through conventional spinnerets according to a known melt spinning process. Strongly lightened polypropylene fibers are obtained.

If, instead of the compound of the formula 58, the compounds of the formulas 54, 67, 79, 81, 82, 92, 98 or 101, good lightening effects are also obtained.

Example 21

A fabric made of polyvinyl chloride fibers is padded at room temperature (about 20 ° C.) with an aqueous dispersion containing 0.1 to 1 g of one of the oxdiazole compounds of the formulas 58, 64, 65, 67, 79, 80 or 94 and 1 g of one per liter Addition product of about 35 moles of ethylene oxide to 1 mole of octadecyl alcohol and dries at about 70 ^° C. The dry material is then subjected to a heat treatment for one minute at 100 C. The fabric of polyvinyl chloride fibers treated in this way has a significantly higher whiteness than an untreated fabric Polyvinyl chloride fibers.

Example 22

A soap (sodium salt of higher fatty acids) is made which contains 0.5% of the compound of formula 37 or 0.5% of the compound of Formula 53 contains.

A polyamide fabric that is washed with one of these soaps at 60 to 70 C for 30 minutes a lighter appearance than the material, which is washed with a soap, which the compound of formula 37 or 53 does not contain.

If, instead of soap, an anionic, nonionic or cationic, liquid or liquid is used solid synthetic detergent, similar whitening effects are obtained.

Claims (6)

Claims: 1. Use of Stflbenyl-1,3,4-oxdiazoles of the formula A ₁ -CH = CH where A | represents a phenyl, naphthyl, diphenylyl, styryl, stilbenyl, thienyl, 2-benzoxazolyl or 2-naphthoxazolyl radical, B represents a phenylene, furoylene and thienylene bridge member, A _{x represents} a phenyl, Diphenylyl or naphthyl radical, R represents hydrogen, halogen, an alkyl, phenyl, carboxyl, sulfonic acid, hydroxyl or amino group and their substitution products A "- CH = CH wherein A _{2 is} a phenyl, naphthyl, diphenylyl, styryl, stilbenyl, thienyl, 2-benzoxazolyl or 2-naphthoxazolyl radical, a terminal phenyl nucleus having one to two alkyl, carbalkoxy, alkoxy or halogen -May contain substituents, B is a 2,5-furoylene, 2,5-thienylene or 1,4-phenylene bridge member, A _y for 1 / or functional derivatives and where terminal phenyl nuclei in the general formula can contain one to two substituents R, where m, η and ρ also represent the values 1 or 2, as optical brighteners for organic materials. 2. Use according to claim 1 of stilbenyl-1,3,4-oxdiazoles the formula Il r-l a naphthyl radical, a diphenylyl radical or a phenyl radical, which may contain an alkyl, carbalkoxy or halogen substituent, and m, η and ρ stand for the numbers 1 or 2. 3. Use according to claim 1 of stilbenyl-1,3,4-oxdiazoles the formula where A is a phenyl, naphthyl, styryl, stilbenyl, thienyl, 2 - benzoxazolyl or 2-naphthoxazolyl radical and B is a phenylene, furoylene or thienylene bridge member and m and η are one or two and the radicals R is hydrogen, halogen, an alkyl, R7 N- -N Il -N 45 represent phenyl, carboxy?, Sulfonic acid, hydroxyl or amino groups and their substitution products or functional derivatives. 4. Use of stilbenyl-1,3,4-oxdiazoles the formula wherein R ₇ and R _{8 are the} same or different and have a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a carboxyl group, a carbalkoxy group having up to 4 carbon atoms in the alkyl group, a chlorine atom, a phenyl group or an alkoxy group —Ν ^ 1 to 4 carbon atoms, as optical brightening agents for polyantiide spinning masses or for mounting and impregnation processes for polyamides. 5. Use of stilbenyl-1,3,4-oxdiazoles the formula CH = CH wherein the Reslc R _{9 are} hydrogen atoms. Denote alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 4 carbon atoms N- R ₉ or one radical R _{9 represents} a phenyl or 2-benzoxazolyl group, while the other radical R _{9 represents} a hydrogen atom, or the two radicals R ₉ together with the phenyl radical on which they are attached to form a naphthyl radical, as an optical brightening agent for polyamide spinning masses. 6. Use of StilbenyM, 3,4-oxdiazoles of the formula CH = CH N N in which R _{10 stands} for a hydrogen atom, a chlorine atom, or an alkyl or alkoxy group with up to 4 carbon atoms each or a phenyl group, as an optical brightener for mounting and impregnation processes for polyamides. 15th